Selective aerobic oxidation reactions using a combination of photocatalytic water oxidation and enzymatic oxyfunctionalizations

Peroxygenases offer an attractive means to address challenges in selective oxyfunctionalization chemistry. Despite this, their application in synthetic chemistry remains challenging due to their facile inactivation by the stoichiometric oxidant H₂O₂. Often atom-inefficient peroxide generation systems are required, which...

Alcohol Dehydrogenases Catalyze the Reduction of Thioesters

Alcohol dehydrogenases are well-established catalysts for various reduction reactions. However, the reduction of carboxylic acid derivatives has not yet been reported with these enzymes. In this contribution, we demonstrated that carboxylic acid thioesters could be readily reduced by a range of alcohol dehydrogenases, albeit at significantly...

Photoelectroenzymatic Oxyfunctionalization on Flavin-Hybridized Carbon Nanotube Electrode Platform

Peroxygenases are very promising catalysts for oxyfunctionalization reactions. Their practical applicability, however, is hampered by their sensitivity against the oxidant (H₂O₂), therefore necessitating in situ generation of H₂O₂. Here, we report a photoelectrochemical approach to provide...

Artificial photosynthesis: Hybrid systems

Oxidoreductases are promising catalysts for organic synthesis. To sustain their catalytic cycles they require efficient supply with redox equivalents. Today classical biomimetic approaches utilizing natural electron supply chains prevail but artificial regeneration approaches bear the promise of simpler and more robust reaction schemes....

Fueling biomass-degrading oxidative enzymes by light-driven water oxidation

Photosynthesis may be described as light-driven oxidation of water and subsequent use of the generated reducing equivalents to fix CO₂ and synthesize higher energy organic compounds, such as carbohydrates. The transposition of the sustainable and atom-efficient strategy of water oxidation to in vitro controlled biocatalytic...

Towards preparative peroxygenase-catalyzed oxyfunctionalization reactions in organic media

The peroxygenase from Agrocybe aegerita (AaeUPO) has been evaluated for stereoselective oxyfunctionalization chemistry under non-aqueous reaction conditions. The stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol was performed in neat substrate as reaction medium together with the immobilized biocatalyst and <sup>tert</sup...

Peroxygenase-catalyzed oxyfunctionalization reactions promoted by the complete oxidation of methanol

Peroxygenases catalyze a broad range of (stereo)selective oxyfunctionalization reactions. However, to access their full catalytic potential, peroxygenases need a balanced provision of hydrogen peroxide to achieve high catalytic activity while minimizing oxidative inactivation. Herein, we report an enzymatic cascade process that employs methanol...

Specific oxyfunctionalisations catalysed by peroxygenases: Opportunities, challenges and solutions

Peroxygenases enable H2O2-driven oxyfunctionalisation of organic compounds such as selective epoxidation, hydroxylation and heteroatom oxygenation. Therefore, peroxygenases are potentially very useful tools for the organic chemist. This contribution reviews the current state of the art in peroxygenases, their availability, engineering and...